There are a number of patents that disclose the use of polymeric supports for olefin polymerization catalysts. Generally the supports are polyolefins as illustrated for example by Atlantic Richfield's U.S. Pat. No. 4,407,727; Quantum's WO 96/35726; and the abstract of Mitsubishi's JP 67407. Polyethylene and polypropylene are not polymers prepared from C4-12 vinyl monomers and thus the references do not teach or disclose the subject matter of the present patent application.
There are a fairly large number of patents which teach using polymeric supports comprising styrene and optionally a cross-linking agent such as divinyl benzene and/or polymeric supports such as poly(methyl methacrylate). These patents are illustrated by U.S. Pat. Nos. 4,623,707; 4,632,912; 5,139,985; 4,900,706; 5,463,000; 5,118,648; 5,498,582; and EP 344 755. However, these references do not teach treating the polymeric support with a halosulfonic acid.
The use of an aluminoxane as a cocatalyst for ethylene polymerization catalyst was reported by Manyik et al. in U.S. Pat. No. 3,231,550.
Subsequently, Kamisky and Sinn discovered that aluminoxanes are excellent co-catalysts for metallocene catalysts, as disclosed in U.S. Pat. No. 4,404,344.
The use of a supported aluminoxane/metallocene catalyst is further described in, for example, U.S. Pat. No. 4,808,561.
The use of fluorided alumina as a support for Phillips type chromium catalysts has been widely disclosed in the patent literature. U.S. Pat. Nos. 5,221,720; 5,221,655; 5,221,654; 5,219,962 and 5,219,817 (all McDaniel et al. and assigned to the Phillips Petroleum Company) relate to this art. Also U.S. Pat. No. 4,100,337 (Noshay et al. assigned to the Union Carbide Corporation) teaches the use of fluorided silica supports for chromium polymerization catalysts.
The Applicants have now discovered that the use of a polymeric support which has been treated with (directly halogenated with) a halosulfonic acid improves the productivity of Group IV metal catalysts which are activated with an aluminoxane activator.